Bactericidal and fungicidal dichloronitro-quinoxalines



United States Patent 3,185,905 BACTERECIDAL AND FUNGHCRDAL DICMQRG- NiTRfi-QUENGXALINES Junnosuke Hattori, Toyonaira-shi, Hiroshi fingiyama Ashiya-shi, Kosuke Yoshioka, Hiralrata-shi, and Seiil Koike, Toyonaira-shi, .iapan, assignors to Surnitonro Chemical Company, Ltd, Osaka, Japan, a corporation of Japan No Drawing. Filed June 17, 1953, Ser. No. 288,444 8 Claims. (Cl. 167-33) This invention relates to microbicidal compositions which are widely utilizable as medicinal and agricultural microbicides. More particularly, the present invention pertains to agricultural and medicinal microbicide com positions containing one or more compounds represented by the general formula wherein X represents a halogen atom and 12 shows an integer of 1 or 2. These compounds are less toxic to warm blooded animals and have microbicidal actions on a broad extent of microorganisms: e.g., plant pathogenic fungi, such as Pzricularz'a oryzae, Alternaria kikuchiana, Ophiobolus mycbeanus, Pythium cphrmidermatum, and Pellicularia filamentosa; bacteria such as Xanthomonas oryzae; human parasitic fungi, such as Triclzoplzyton rubrum, Trichophyton tonsurans, and Trichophyton ment czgrophytes; and bacteria such as Staphylococcus aureus and Escherichia coli. Therefore, the preparations obtained by mixing one or more of the above compounds with a suitable adjuvant can protect plant or human from the attack of said pathogenic fungi and bacteria safely and economically.

V The compounds represented by the above Formula I may be prepared either by reacting phosphorus pentahalide or phosphorus oxyhalide, or by reacting phosphorus pentahalide in phosphorus 'oxyhalide or phosphorus trihalide, with a compound represented by the general formula J, 0 (III) wherein n is an integer of 1 or 2. Also, the effective compounds prepared by the above process havg the In actual use, the present microbicidal compositions are employed, for agricultural applications, in the form Patented dune 1, 1955 of preparations of emulsions, wettable powders, dusts, while for medicinal applications, in the form of preparations dusting powders, ointments and paints. The compositions for agricultural use are prepared in the following manners: Namely, the dusts are prepared by thoroughly mixing and pulverizing the active ingredients, i.e., the present compound, with one or more members selected from the group consisting of talc, bentonite, attaclay, kaolin, and diatomite. The wettable powders may be formed by thoroughly mixing two members of the active ingredient and a wetting agent or three members of the active ingredient, a wetting agent, and one member selected from the group consisting of talc, bentonite, kaolin, attaclay, vermiculite and diatomite. The emulsions are prepared by mixing the present active ingredient with an emulsifier and a solvent which well dissolves the two to form a homogeneous liquid. Further, the compositions for medicinal use are prepared by the following processes in addition to those described in the examples shown later. Namely, the ointments are prepared by dissolving the present active ingredient in, or thoroughly mixing it with one or more members selected from the group consisting of animal and vegetable fats and oils, paraflinic hydrocarbons, such as wax, Vaseline and liquid parafiin, silicon, carbowax, lanolin, plastics, glycols, higher alcohols, glycerine, water and surface active agents. The dusts are prepared by mixing and pulverizing the present active ingredient with one or two members selected from the group consisting of kaolin, diatomite, starch and zinc white. The paints are prepared by dissolving the present active ingredient in, or homogeneously mixing it with one or more members a selected from the group consisting of water, ethanol, fatty oils, glycerine, soaps, surface active agents and suspending agents.

The following examples illustrate the present invention:

EXAMPLE 1 2() parts or" 2,3-dichloro-6-nitro-quinoxaline, 20 parts of Triton X-17'7 (trade name of a produce of Rohm and Haas Co), 20 parts of oi-methylnaphthalene, and 10 parts of dioxane are thoroughly mixed to form a homogeneous agricultural emulsion containing 20% of active ingredient.

EXAMPLE 2 EXAMPLE 3 1 part of 2,3-dichloro-5,7-dinitro-quinoxaline and 99 parts of talc are thoroughly mixed and pulverized to prepare an agricultural dust containing 1% of active ingredient.

EXAMPLE 4 0.5 part of 2,3-dichloro-6-nitro-quinoxaline and 05 part of 2,3-dichloro-5,7-dinitro-quinoxaline are added to 99 parts of Plastibase (a mixture of polyethylene and liquid paraffin, trade name of the product of :E. R. Squibb & Sons Co.) and thoroughly kneaded to prepare on ointment useful for medicinal application.

EX MPLE 5 1 part of 2,3-dichloro-S-nitro-quinoxaline is dissolved in 99 parts of 2-methyl-2,4-pentane-diol to prepare a medicinal paste useful for external applications.

EMMPLE 6 1 part of 2,3-dichloro-5,7dinitro-quinoxaline and 99 parts of medicinal talc are thoroughly mixed and pulverized to prepare a dusting powder useful for medicinal applications.

When the products shown in the above examples are actually used: for example, the agricultural emulsion of Example 1 is employed by diluting it with water to 1,000 times and spraying 40 l. of the diluted emulsion per a, rice blast occurring in paddy-fields can be prevented almost completely. Also, athletes foot can be cured by applying the ointment of Example 4 to the afifected parts.

The effects of the thus obtained microbicides on plant pathogenic microorganisms are shown in' the following 7 tables. 'Tests were carried out according to slide-germination method (refer to Phytopathology, vol. 37, page 354) and mycelia-groWth-inhibiting test method on an agar plate. The latter test method is conducted by charging an agar medium containing the corresponding microbicide into a Fetri dish to form an agar plate, and inoculating in the center of the plate a colony of previously cultured test-microorganisms and observing the growth of the microorganism. The concentrations in the tables are those of active ingredients shown by p.p.m. unit.

Table 3. Resnlts obtained by flower pot test Numbers of spots Affected per leaf Compound Concenleaves tration (percent) 1 Develop- Total ing spots spots 2,3-dichloro-6-nltro- {x 4, 000 9 0.14 0.18 quinoxaline x 16,000 73 0.53 1.75 2,3-diehloro-5,7-dinitro- {x 4, 000 7 0. 16 0.19 quinoxaline. x 16,000 60 0. 1. 22 2,3-diohloro-5-n {x 4, 000 7 0. 21 0.29 quinoxaline; x 16,000 71 0.80 0.93 No treatment. 79 3. 40 5. 98

' Table 4 shows the microbicidal activities of the pres- 1 out compounds; eitected by agar dilution method, against human parastic microorganism such as the fungi of Trichophytongenus, Staphylococcus aureans, and Escherichia coli. used, while for others, bouillon agar media.

The concentrations for the complete growth inhibition are those of active ingredients shown by ppm. unit. The control employed was presently marketed 2-naphthyl ester of N-methyl-N-(1-naphthyl)-thionocarbamie acid.

Table 1. Res ultr obtained by slide-germination method (LC value) Pirlculana Aliemaria Ophz'obolus oryzae kikucln'ana myabeamts 2,3-dichloro-6-nitro-quinoxaline 1. 0 1. O 2. 0 2,3-dichloro-5,7-di nitroquinoxaline 0. 5 0. 5 1. 0 2,3-dichloro-5-nitroquinoxaline 1. 0 1.0

Table 2.--Result obtained by mycelia-growth-inhibiting- The fungistatic activity'of the novel compounds ex amined was determined by means of the. agar-dilution method. This method consists in principleof incubating apotato-agar medium containing a known amount of the fungicide with fungus spore. After six days of incubation presence or absence of growth is observed visually. The minimum concentration causing complete inhibition 20 of growth is read.

The results obtained are presented in Table 5 below.

test (concentration required for complete inhibition) 2,3-dichl0ro-G-nitro-qninoxaline.. 2,3-dichloro-5,7-dinitro-quinoxpots of about 10 cm. in diameter.

Pythz'um apham'dermatum Pellz'cularia filamentosa Corticinm sasalm Botrytv's' cinerea Further, the results obtained by the flower pot test are 1 shown below, Namely, the miorobicides were sprayed to rice plantsat a 3-4' leaves stage cultivated in flower One day after the spray, the spores of Riricularia oryzae were inoculated, and 5 days after the inoculation, the number of spots on the leaves were counted. No phytotoxicity due to the microbicides were observed at any concentrations.. The

concentrations show dilution multiples of active ingredients. 1

2,3-dichloro-5,7-dinitroqnihoxaline.

Table 5 Minimum concentration causing complete inhibition growth, p.p.m.

Compound GZom. cingulata Clado.

f l C'ercospora u 1mm beticola 2,3fdichloro-fi-nitroquinoxaliue 5: 2,3-dichloro-5-nitroquinoxaline .u 1(5) For Trichophyton, Sabouraud. agar media were What we claim is:

1. A method for protecting plants from attack of microorganisms which comprises contacting said plants With a microbicide containing as active ingredients at least one of the compounds represented by the formula /N\ or (N02)n l:

l; or

wherein n is an integer of from 1 to 2.

6. An emulsion comprising -80% by weight of a solvent, 10-30% by weight of dispersing agents and 10- 50% by Weight of active microbicidal ingredients consisting of at least one of the compounds represented by the formula:

wherein n is an integer of from 1 to 2.

7'. Wettable powders comprising 5-85% by weight of a carrier in a powder form, 540% by weight of dispersing agents, and 10-90% by weight of active microbicidal ingredients consisting of at least one of the compounds represented by the formula:

\N Cl wherein n is an integer of from 1 to 2.

8. A method for destroying fungi and bacteria comprising contacting the same with a microbicide containing as active ingredients at least one of the compounds represented by the formula:

N o1 Noon wherein n is an integer of from 1 to 2.

References Cited by the Examiner Chemical Abstracts (I) 53:13l60h (1959).

Chemical Abstracts (II) 53:16142th (1959). Chemical Abstracts (III) 55:18741f (1961). Chemical Abstracts (IV) 57z8l6-818 (1962).

JULIAN S. LEVITT, Primary Examiner.

LEWIS GOTTS, Examiner. 

1. A METHOD OF PROTECTING PLANTS FROM ATTACK OF MICROORGANISMS WHICH COMPRISES CONTACTING SAID PLANTS WITH A MICROBICIDE CONTAINING AS ACTIVE INGREDIENTS AT LEAST ONE OF THE COMPOUNDS REPRESENTED BY THE FORMULA 